Electrically conductive composition of polyheteroaromatic compounds and polymeric sulfates

ABSTRACT

A composition comprising (a) at least one oxidized polycationic polyheteroaromatic compound and (b) at least one polyanion of a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR1## in repeating structural units. The composition has high electrical conductivity and good mechanical properties, especially after drawing at temperatures below the melt/decomposition temperature. The material may be used as electrodes, electrically conductive filaments or components for electromagnetic screening.

.Iadd.This application is a reissue of Ser. No. 07/401,352 filed Aug.31, 1989 now U.S. Pat. No. 5,061,401. .Iaddend.

The present invention relates to a composition comprising (a) at leastone oxidised polycationic polyheteroaromatic compound and (b) at leastone polyanion of a film-forming thermoplastic polymer containingsulfated alcohol groups ##STR2## in repeating structural units, to aprocess for the preparation of said composition, to a method ofincreasing the electrical conductivity of said composition and to theuse of the composition as electrically conductive material.

It is known to obtain electrically conductive salts of polycationicpolyheteroaromatic compounds by electrochemical polymerisation ofheteroaromatic compounds, especially pyrrole, in the presence ofnonnucleophilic anions. The mechanical properties of such salts ofpolyheteroaromatic compounds, which are normally deposited as film onanodes, are insufficient for many applications.

To improve the mechanical properties it has been proposed to usecompositions of doped polyheteroaromatic compounds in non-conductivepolymers. Reference is made in this connection to the followingpublications: Synthetic Metals, 22 (1987), 145-156; J. of Polym.Science: P.C.E., 23 (1985), 1687-1698, Bull. Chem. Soc. Jpn., 60,3315-3320 (1987) and European patent application 0 191 726. To avoid theconcurrent use of dopants, the concurrent use of non-nucleophilic anionsin the electrochemical polymerisation has been proposed, for examplepolystyrene sulfonates, polyvinyl sulfonates (q.v. for example Europeanpatent specification 0 129 070 and U.S. Pat. No. 4 552 927) or latices(q.v. Synthetic Metals, 15 (1986), 175-182).

Porous compositions of polypyrrole with, for example, alkylsulfates aredisclosed in German Offenlegungsschrift 3 402 133. It is mentioned thatsulfates containing polymeric radicals can also be used. A film-formingcomposition of polypyrrole and a chlorosulfonated polyvinyl alcohol isdisclosed in GB patent specification 2 124 635. Although the dry filmhas good conductivity, it is described as tough but brittle, and hencedoes not have sufficient mechanical strength.

There is a need to provide electrically conductive polymer compositionswhich can be processed by methods of thermoplastic processing, forexample compression moulding or stretch forming, and which have goodmechanical properties such as good tensile and flexural strength. Itwould also be useful if the electrical conductivity and the mechanicalproperties could be substantially improved by such a processing method.

In one of its aspects, the invention relates to a composition comprising

a) at least one polyheteroaromatic compound or an aniline in oxidised,polycationic form, and

b) at least one polyanion of a film-forming thermoplastic polymercontaining sulfated alcoholic groups ##STR3## in repeating structuralunits.

Polyheteroaromatic compounds will be understood within the scope of thisinvention as meaning homopolymers and copolymers which contain repeatingheteroaromatic structural units. They may be high molecular or alsooligomeric, provided they are solid at room temperature and are able toform films. Preferred polyheteroaromatic compounds are those of 5- to6-membered rings which contain 1 to 3 hetero atoms, preferably 1 heteroatom, selected from the group consisting of --O--, --S--and --N--, andthe carbon atoms of which are unsubstituted or substituted by C₁ -C₁₆alkyl, preferably C₁ -C₁₂ alkyl. Preferably two carbon atoms are notsubstituted, so as to be able to carry out the electrochemicalpolymerisation. The 5- or 6-membered ring is preferably selected fromthe group consisting of pyrrole, thiophene, furan, 2,2'-bipyrrole,2,2'-bithiophene, 2,2'-bifurane, thiazole, oxazole, thiadiazole andimidazole.

Especially preferred is the polyheteroaromatic compound of a pyrrole offormula ##STR4## wherein R² and R² are each independently of the otherhydrogen or C₁ -C₁₆ alkyl. R¹ and R² may be C₁ -C₁₂ alkyl, for examplemethyl or ethyl, and are preferably hydrogen. The NH-- group of thepyrrole may be substituted by C₁ -C₁₂ alkyl, preferably C₁ -C₆ alkyl.

Anilines may be aniline itself and aniline which is substituted in3-position by C₁ -C₁₂ alkyl, preferably C₁ -C₆ alkyl.

The composition of this invention contains, in each structural unit ofthe polyheteroaromatic compound, preferably 0.1 to 0.5, most preferably0.2 to 0.4, structural units containing sulfated alcohol groups ##STR5##

The thermoplastic polymer eligible for use in the composition of thisinvention containing sulfated alcoholic groups ##STR6## in salt formpreferably has a glass transition temperature of -100° to +350° C., moreparticularly -50° to +250° C., measured by differential scanningcalorimetry. (DCS).

The tensile strength of these thermoplastic polymers is preferably notless than 5 MPa, especially not less than 20 MPa, determined accordingto DIN 53 455. Depending on the nature of the polymer, the tensilestrength can be up to 1000 MPa, preferably up to 500 MPa and, mostpreferably, up to 300 MPa. The sulfated alcohol groups in salt form maybe, for example, alkali metal and ammonium salts, which are hereinafterdescribed for the polymers.

The ratio of free alcoholic groups to sulfated alcohol groups ##STR7##in the thermoplastic polymer can be, for example, from 50:1 to 1:50,preferably from 10:1 to 1:10.

The sulfated alcohol groups may be present in the terminal position assecondary ##STR8## groups in the polymer backbone or as primary --CH₂--O--SO₃.sup.⊖ groups in side-chains of the polymer, or in the centralposition as secondary ##STR9## groups or as tertiary ##STR10## groups.

The thermoplastic polymers may be derived from polymers or mixturesthereof which contain different hydroxyl groups, for example polyesters,polyester amides, polyurethanes, polyamides, polycarbonates andpolyimides obtained from hydroxyl-containing monomers, saponifiedpolymers of vinyl esters or ethers, hydroxylated polyolefins such aspolybutadiene, polyisoprene or chloroprene, polyacrylates orpolymethacrylates containing hydroxyl groups in the ester moiety,polysiloxanes containing hydroxyalkyl groups or reduced polyketones orcopolymers thereof; as well as copolymers of vinyl alcohol, acrylates ormethacrylates or diolefins with comonomers such as acrylonitrile,olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride,vinylidene fluoride, styrene, α-methylstyrene, maleic anhydride,maleimide, vinyl ethers and vinyl esters.

The sulfated thermoplastic polymers are preferably derived from polymersselected from the group consisting of polyadducts of glycidyl compoundscontaining on average more than one epoxy group with a diol;homopolymers and copolymers of hydroxyalkyl acrylates and methacrylates;homopolymers and copolymers of butadiene, isoprene and chloroprene whosedouble bonds are hydroxylated; polyimides of hydrogenatedketotetracarboxylic acids, especially benzophenonetetracarboxylic acids;hydroxyalkyl polysiloxanes; and polyesters, polyamides, polyurethanesand polyimides from C₄ -C₁₂ -alkenylenediols or C₄ -C₁₂alkenylenediamines whose double bond is hydroxylated.

The thermoplastic polymer may be, for example, an at least partiallysulfated polyadduct of a) a glycidyl compound containing on average morethan one epoxy group and b) a diol which contains ##STR11## groups inthe polymer chain.

The polyadducts are preferably derived from glycidyl compoundscontaining on average two epoxy groups in the molecule.

Particularly suitable glycidyl compounds are those containing twoglycidyl, β-methylglycidyl or 2,3-epoxycyclopentyl groups attached to ahetero atom (for example a sulfur atom, preferably an oxygen or anitrogen atom). Such compounds are in particular:bis(2,3-epoxycyclopentyl)ethers; diglycidyl ethers of polyhydricaliphatic alcohols such as 1,4-butanediol, or polyalkylene glycols suchas polypropylene glycols; diglycidyl ethers of cycloaliphatic polyolssuch as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethers ofpolyhydric phenols such as resorcinol, bis(hydroxyphenyl)methane,2,2-bis(p-hydroxyphenyl)propane (diomethane),2,2-bis(4'-hydroxy-3',5'-dibromophenyl)propane,1,3-bis(p-hydroxyphenyl)ethane; bis(β-methylglycidyl)ethers of theabove-mentioned dihydric alcohols or dihydric phenols, diglycidyl estersof dicarboxylic acids such as phthalic acid, terephthalic acid, Δ⁴-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylderivatives of primary amines and amides and heterocyclic nitrogen basescontaining two nitrogen atoms, and N,N'-diglycidyl derivatives ofdisecondary diamides and diamines such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N-diglycidyl-p-aminophenylmethyl ether,N,N'-dimethyl-N,N'-diglycidyl bis(p-aminophenyl)methane;N',N"-diglycidyl-N-phenylisocyanurate; N,N'-diglycidylethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropylhydantoin,N,N-methylene-bis(N',N'-diglycidyl-5,5-dimethylhydantoin),1,3-bis(N-glycidyl-5,5-dimethylhydantoin)-2-hydroxypropane;N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil.

The glycidyl compounds can be reacted with aliphatic, cycloaliphatic oraromatic diols to the preferred polyadducts, in which reaction asecondary alcohol group is formed at the glycidyl group e can besulfated.

The glycidyl compounds can also be reacted with primary aliphatic,cycloaliphatic or aromatic monoamines (for example aniline, toluidine,C₁ -C₁₂ alkylamines, C₂ -C₁₂ hydroxyalkylamines), aliphatic,cycloaliphatic or aromatic dicarboxylic acids (for example maleic acid,adipic acid, trimethyladipic acid, sebacic acid, azelaic acid,succininic acid, dodecylsuccinic acid, phthalic acid, terephthalic acid,Δ⁴ -tetrahydrophthalic acid, hexahydrophthalic acid,4-methylhexahydrophthalic acid, 3,6-endomethylene-Δ⁴ -tetrahydrophthalicacid, 4-methyl-3,6-endomethylene-Δ⁴ -tetrahydrophthalic acid), or withaliphatic, cycloaliphatic, heterocyclic or aromatic di-secondary aminesor di-secondary carboxamides (for example N,N'-dimethylethylenediamine,N,N'-dimethylpropylene-1,3-diamine, N,N'-dimethylhexamethylenediamine,N,N'-dicyclohexylhexamethylenediamine,N,N',N"-trimethyldiethylenetriamine, N,N'-diethylpropylene-1,3-diamine,N-methyl-3,5,5-trimethyl-3-(methylaminomethyl)cyclohexylamine,N,N'-dimethylated or -N,N'-diethylated aromatic diamines, for example m-or p-phenylenediamine, bis(4-aminophenyl)methane or -sulfone,2,2-bis(4-aminophenyl)propane, N,N-dimethyl-m-xylylenediamine, as wellas ethyleneurea, 5,5-dimethylhydantoin, 5-isopropylhydantoin,N,N-methylenebis-5,5-dimethylhydantoin,1,3-bis(5,5-dimethyl)-2-hydroxypropane,5,5-dimethyl-6-isopropyl-5,6-dihydrouracil), by polyaddition to givelinear polyadducts.

A preferred composition of this invention is one in which the polyadductcontains

a) 100 to 5 mol % of identical or different structural units of formulaI ##STR12## and

b) 95 to 0 mol % of the identical or different structural units offormula II ##STR13## based on said polyadduct, in which formulae (I) and(II) above R³ and R⁴ are each independently of the other the radical ofa diol containing aliphatic or aromatic diol groups, which radical isdiminished by two hydroxyl groups, and R' is hydrogen, C₁ -C₂₀ alkyl, C₁-C₂₀ acyl or aminocarbonyl which is N-substituted by a C₁ -C₂₀hydrocarbon radical.

Preferably the polyadduct contains 90 to 20 mol %, preferably 30 to 80mol %, of structural units of formula I, and 80 to 10 mol %, preferably70 to 20 mol %, of structural units of formula II.

In a preferred embodiment of the invention, R³ and R⁴ are identicalradicals. R³ and R⁴ as a radical having aliphatic diol groups containspreferably 2 to 12, most preferably 2 to 8 carbon atoms. The hydroxylgroups may be attached to open-chain or cyclic aliphatic radicals. Asuitable aliphatic radical is typically linear or branched C₂ -C₁₂-alkylene, C₃ -C₈ cycloalkylene, C₁ -C₄ alkyl-C₆ --C₈ cycloalkyl,cyclohexylmethylene or cyclohexyldimethylene. Illustrative examples ofsuch radicals are ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or1,4-butylene, 1,2-, 1,3-, 1,4- or 1,5-pentylene, 1,2-, 1,3-, 1,4-, 1,5or 1,6-hexylene, heptylene, octylene, nonylene, decylene, undecylene,dodecylene, 1,3-cyclopentylene, 1,3-or 1,4-cyclohexylene,2-methyl-1,4-cyclohexylene and cyclohexyl-1,4-dimethylene.

The aromatic diol groups of the diols used for the polyadducts arepreferably phenolic groups. The diol radicals carrying phenolic groupscontain preferably 6 to 30, most preferably to 6 to 20, carbon atoms. Apreferred embodiment of the invention relates to compositions wherein R³and R⁴ are each independently of the other a radical of formula III##STR14## wherein X is a direct bond, C₁ -C₄ alkylene, C₂ -C₁₂alkylidene, C₅ -C₈ cycloalkylidene, --O--, --S--, --SO--, SO₂ --,--CO--, --CO₂ --, --N(C₁ -C₄ alkyl) or --Si(CH₃)₂, R⁵ and R⁶ are eachindependently of the other hydrogen, halogen, C₁ -C₄ alkyl, or C₁ -C₄alkoxy, and x is 1 or 2 and y is 0 or 1.

X is preferably a direct bond, methylene, ethylene, C₂ -C₆ alkylidene.cyclohexylidene or cyclopentylidene, --O--or --S--. R⁵ and R⁶ arepreferably hydrogen or methyl, and Y is preferably 1.

Preferably R³ and R⁴ are the radical ##STR15## A further preferredcomposition of the invention is one in which the thermoplastic polymeris an at least partially sulfated homopolymer or copolymer of acrylatesor methacrylates containing a ##STR16## group in the ester moiety. Apreferred composition of this type is one in which the polymer contains

a) 100 to 5 mol % of identical or different structural units of formulaIv ##STR17## and

b) 95 to 9 mol % of identical or different structural units of formula V##STR18## based on said polymer, in which formulae (IV) and (v) R⁷ ishydrogen or methyl, R⁸ is linear or branched C₂ -C₁₈ -alkylene, poly(C₂-C₆ oxaalkylene) containing 2 to 6 oxaalkylene units, C₅ -C₈cycloalkylene, phenylene, benzylene or xylylene or is the group##STR19## Y is --O--, ##STR20## or --N(C₁ -C₄ alkyl), and R¹² is C₁ -C₁₈alkyl, C₅ -C₇ -cycloalkyl, C₁ -C₁₂ alkyl)-C₅ -C₇,cycloalkyl, phenyl, (C₁-C₁₂ alkyl)phenyl, benzyl or (C₁ -C₁₂ alkyl)benzyl, R⁹ is hydrogen, C₁-C₆ alkyl, --COOR¹² or --COO.sup.⊖, R¹⁰ is hydrogen, fluoro, chloro,cyano or C₁ -C₆ alkyl, and R¹¹ is hydrogen, fluoro chloro, cyano, R¹² is--O--, C₁ -C₁₂ alkyl, --COO.sup.⊖, --COOR¹², --COOR⁸ --OH, --OCO--R¹² orphenyl, where R⁸ and R¹² have the given meanings.

Preferably the polymer contains 90 to 20 mol %, most preferably 80 to 30mol %, of structural units of formula IV, and 80 to 10 mol %, mostpreferably 70 to 20 mol %, of structural units of formula V.

R⁸ as alkylene contains preferably 2 to 12, more particularly 2 to 8and, most preferably, 2 to 6, carbon atoms. Illustrative examples ofsuch groups are ethylene and the isomers of propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tetradecylene, hexadecylene, and octadecylene.Preferred groups are ethylene, 1,2- and 1,3-propylene, 1,2-, 1,3- and1,4-butylene, 1,2-, 1,3-, 1,4-and 1,5-pentylene, and 1,2-, 1,3-, 1,4-,1,5- and 1,6-hexylene. R⁸ as poly(oxaalkylene) preferably contains 2 to4 oxaalkylene units and preferably 2 to 4, most preferably 2 or 3,carbon atoms in the alkylene moiety.

R⁸ as cycloalkylene is preferably cyclopentylene or cyclohexylene.

Polymers in which R⁸ is the group ##STR21## are reaction products ofglycidyl esters of poly- or copoly(meth)acrylic acid with a compound R¹²-Y-H which contains active hydrogen.

Y is preferably --O-- ode ##STR22## R¹² may be linear or branched alkylof 1 to 18, preferably 1 to 12 most preferably, 1 to 6, carbon atoms.R¹² as cycloalkyl is preferably cyclopentyl or cyclohexyl. Where R¹² is(C₁ -C₁₂ alkyl)cycloalkyl, the cycloalkyl moiety is preferablycyclopentyl or cyclohexyl, and the alkyl moiety may be linear orbranched and contains preferably 1 to 6, most preferably 1 to 4, carbonatoms. Where R¹² is alkylphenyl or alkylbenzyl, the alkyl moiety may belinear or branched and contains preferably 1 to 6, most preferably 1 to4, carbon atoms.

R⁹ is preferably hydrogen. R⁹ as alkyl is preferably methyl or ethyl.Where R⁹ is --COOR¹², R¹² is preferably C₁ -C₁₂ alkyl, most preferablyC₁ -C₆ alkyl.

R¹⁰ as alkyl is preferably C₁ -C₄ alkyl, typically methyl, ethyl,n-propyl and n-butyl. R¹⁰ is preferably hydrogen, chloro or C₁ -C₄alkyl.

Where R¹¹ is the group R¹² --O--, R¹² is preferably C₁ -C₁₂ alkyl,preferably C₁ -C₆ alkyl. An alkyl group R¹¹ preferably contains 1 to 6,most preferably 1 to 4, carbon atoms. Where R¹¹ is the group --COOR¹²,R¹² is preferably C₁ -C₁₂ alkyl, most preferably C₁ -C₆ alkyl,cyclopentyl or cyclohexyl. Where R¹¹ is the group --OCO--R¹², R¹² ispreferably C₁ -C₁₂ alkyl, most preferably C₁ -C₆ alkyl, phenyl orbenzyl.

Where R¹¹ is the group --COOR⁸ --OH, R⁸ has the preferred meaningsassigned to it previously.

In a preferred embodiment of the invention, R⁹ is hydrogen, fluoro,chloro, methyl or ethyl, and R¹¹ is fluoro, chloro, cyano, C₁ -C₄ alkyl,C₁ -C₆ alkoxy, --COO--C₁ -C₆ alkyl, --COO--R⁸ --OH, --OCC--C₁ -C₆ alkylor phenyl.

R' as C₁ -C₂₀ alkyl may be linear or branched. R' as acyl may be C₁ -C₂₀-alkyl--CO--, C₅ -C₈ -cycloalkyl--CO--, C₁ -C₁₅ -alkyl-C₅ -C₈-cycloalkyl--CO, C₅ -C₈ -cycloalkyl-CH₂ --O--, C₁ -C₁₄ -alkyl-C₅ -C₈-cycloalkyl--CH₂ CO, phenyl--CO, benzyl--CO, C₁ -C₁₄ -alkylphenyl--CO--or C₁ -C₁₄ alkylbenzyl--CO. The hydrocarbon radical radical in theaminocarbonyl may be C₁ -C₂₀ --alkyl--, C₅ -C₈ --cycloalkyl, C₁ -C₁₅-alkyl--C₅ -C₈ -cycloalkyl--, C₅ -C₈ --cycloalkyl--CH₂ --, C₁ -C₁₄-alkyl-C₅ -C₈ -cycloalkyl--CH₂ --, phenyl, benzyl, C₁ -C₁₄ -alkylphenylor C₁ -C₁₄ alkylphenyl or C₁ -C₁₄ alkylbenzyl. R' is preferablyhydrogen.

Particularly preferred compositions are those wherein the polymercontains structural units of formula IV in which R⁷ is hydrogen or CH₃,and R⁸ is linear or branched C₂ -C₆ alkylene, cyclopentylene orcyclohexylene, and structural units of formula V wherein R⁹ is hydrogen,R¹⁰ is hydrogen or methyl, and R¹¹ is --COOR¹² or --COOR⁸ --OH.

A further preferred embodiment of the invention relates to compositionswherein the thermoplastic polymer is an at least partially sulfatedpolyvinyl alcohol or polyvinyl alcohol copolymer containing ##STR23##groups. Preferably the composition contains polyvinyl alcoholcopolymers.

Preferred compositions are those wherein the copolymer contains

a) 90 to 5 mol % of structural units of formula VI ##STR24## and

b) 95 to 10 mol % of identical or different structural units of formulaV ##STR25## in which formulae (VI) and (V) R⁹, R¹⁰ and R¹¹ have themeanings assigned to them above.

Preferably the copolymer contains 70 to 10 mol %, most preferably 60 to20 mol %, of structural units of formula IV, and 30 to 90 mol %, mostpreferably 40 to 80 mol %, of structural units of formula V.

In formula V, R⁹, R¹⁰ and R¹¹ have the preferred meanings previouslyassigned to them.

Especially preferred compositions are those wherein R⁹ and R¹⁰ arehydrogen and R¹¹ is --OCOR¹², wherein R¹² is C₁ -C₁₈ alkyl, C₅ -C₇-cycloalkyl, (C₁ -C₁₂ alkyl)C₅ -C₇ cycloalkyl, phenyl, benzyl, (C₁ -C₁₂alkyl)phenyl or (C₁ -C₁₂ alkyl)benzyl.

The polyanions of component b) in the compositions of this invention arderived from polymeric salts which are known or obtainable by methodswhich are known per se. These salts are film-forming thermoplasticpolymers containing sulfated alcohol groups --C--O--SO₃.sup.⊖ M.sup.⊕ inrepeating structural units, in which M.sup.⊕ is an alkali metal cationor ammonium cation.

The sulfated alcohol groups may be present as secondary ##STR26## groupsin the polymer backbone, or in terminal position as primary --CH₂--SO₃.sup.⊖ M.sup.⊕ groups in side-chains of the polymer, or in centralposition as secondary ##STR27## groups or as tertiary ##STR28## groups.

The glass transition temperature of the polymers can be from -100 to+350° C., preferably from -50° to +250° C., measured by the DSC. Thetensile strength is preferably not less than 5 MPa, most preferably 10MPa, determined in accordance with DIN 53 455. Depending on the natureof the polymer, the tensile strength may be up to 1000 MPa, preferablyup to 500 MPa and, most preferably, up to 300 MPa.

The degree of polymerisation of the polymers may be, for example, from 5to 10 000, preferably from 10 to 5 000 and, most preferably, from 10 to1000.

Preferred polymers are those wherein the ratio of free alcohol groups tosulfated alcohol groups in the polymer is from 50:1 to 1:50, preferablyfrom 10:1 to 1:10.

The ammonium cation may be NH₄.sup.⊕, a protonated primary, secondary ortertiary amine, or quaternary ammonium or pyridinium. The primary aminemay contain 1 to 18 carbon atoms, preferably 1 to 12 and, mostpreferably, 1 to 6, carbon atoms, the secondary amine may contain 2 to24 carbon atoms, preferably 2 to 12 and, most preferably 2 to 8, carbonatoms, the tertiary amine may contain 3 to 30 carbon atoms, preferably 3to 18 and, most preferably 3 to 12, carbon atoms, and the quaternaryammonium may contain 4 to 36 carbon atoms, preferably 4 to 24 and, mostpreferably 4 to 18, carbon atoms.

Preferred polymers are those wherein M.sup.⊕ is Li.sup.⊕, Na.sup.⊕ orK.sup.⊕, or is R¹³ R¹⁴ R¹⁵ R¹⁶ N.sup.⊕, wherein R¹³, R¹⁴, R¹⁵ and R¹⁶are each independently of one another hydrogen, unsubstituted orhydroxyl-substituted C₁ -C₁₈ -alkyl, phenyl, (C₁ -C₁₂ alkyl)phenyl, (C₁-C₁₂ alkyl)benzyl, C₅ -C₇ -cycloalkyl, (C₁ -C₁₂ -alkyl)-C₅ -C₇-cycloalkyl, or R¹³ und R¹⁴, when taken together, are tetramethyhlene,pentamethylene or 3-oxapentylene, and R¹⁵ and R¹⁶ have the abovemeanings. A preferred embodiment of the invention relates to polymerswherein at least one of R¹³ to R¹⁶ is not hydrogen.

Alkyl groups R¹³ to R¹⁶ may be linear or branched and contain preferably1 to 12, most preferably 1 to 6, carbon atoms. Illustrative of suchgroups are methyl, ethyl, n- and isopropyl, n-butyl, isobutyl andtert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,tetradecyl, hexadecyl and octadecyl.

Hydroxyalkyl groups R¹³ to R¹⁶ may be linear or branched and containpreferably 2 to 18, more particularly 1 to 12 and, most preferably, 2 to6, carbon atoms. Typical examples are 2-hydroxyeth-1-yl, 1- or2-hydroxyprop-3-yl, 1-hydroxybut-4-yl and 1-hydroxyhex-6-yl.

Exemplary of alkylphenyl and alkylbenzyl are methylphenyl,dimethylphenyl, ethylphenyl, n- or isopropylphenyl, n-, iso- ortert-butylphenyl, hexylphenyl, octylphenyl, decylphenyl, dodecylphenyland suitably alkylated benzyl radicals

R¹³ to R¹⁶ as cycloalkyl are preferably cyclopentyl or cyclohexyl.

R¹³ to R¹⁶ as alkylcycloalkyl are preferably (C₁ -C₁₂ -alkyl)cyclopentylor (C₁ -C₁₂ alkyl)cyclohexyl.

Most preferably, R¹³ to R¹⁶ are C₁ -C₆ -alkyl.

The polymers may be derived from different hydroxyl group containingpolymers, for example polyesters, polyester amides, polyurethanes,polyamides, polycarbonates and polyimides obtained from hydroxyl groupcontaining monomers, saponified polymers of vinyl esters or ethers,hydroxylated polydiolefins such as polybutadiene, polyisoprene orchoroprene, polyacrylates or polymethacrylates containing hydroxyalkylgroups in the ester moiety, polysiloxanes containing hydroxyalkyl groupsor reduced polyketones or copolymers thereof; and also copolymers ofvinyl alcohol, acrylates or methacrylates or diolefins with comonomers,for example acrylonitrile, olefins, diolefins, vinyl chloride,vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene,α-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinylesters.

Such polymers are known or can be prepared by commonly known methods.Depending on the nature of the polymer and of the process conditions,hydroxyl groups in the monomers employed are protected by customaryprotective groups.

In a preferred embodiment of the invention, the polymers are an at leastpartially sulfated polyadduct of a) a glycidyl compound containing onaverage more than one epoxy group and (b) a diol which contains##STR29## groups in the polymer chain. Preferred polyadducts arepreviously mentioned herein. Such polymers are disclosed in U.S. Pat.No. 3 402 221.

Preferred polyadducts are those wherein the polyadduct contains a) 100to 5 mol % of identical or different structural units of formula I##STR30## and

b) 95 to 0 mol % of identical or different structural units of formulaII ##STR31## based on the polyglycidyl ether, in which formulae (I) and(II) above R³ and R⁴ are each independently of the other the radical ofa diol containing aliphatic or aromatic diol groups, which radical isdiminished by two hydroxyl groups, and R' is hydrogen, C₁ -C₂₀ alkyl, C₁-C₂₀ acyl or aminocarbonyl which is N-substituted by a C₁ -C₂₀hydrocarbon radical.

Especially preferred polyadducts are those wherein R³ and R⁴ are eachindependently of the other a radical of formula III ##STR32## wherein Xis a direct bond, C₁ -C₄ alkylene, C₂ -C₁₂ alkylidene, C₅ -C₈cycloalkylidene, --O--, --S--, --SO--, SO₂ --, --CO--, --CO² --, --N(C₁-C₄ alkyl) or --Si(CH₃)₂, R⁵ and R⁶ are each independently of the otherhydrogen, halogen, C₁ -C₄ alkyl, or C₁ -C₄ alkoxy, and x is 1 or 2 and yis 0 or 1.

Preferably R³ and R⁴ are the radical ##STR33## R³, R⁴, R⁵, R⁶, X, y andx have the preferred meanings previously assigned to them, and thepreferred content of structural units is likewise as previouslyindicated.

A further preferred embodiment of the invention relates to thosepolymers in which the thermoplastic polymer is an at least partiallysulfated homopolymer or copolymer of acrylates or methacrylatescontaining a ##STR34## group in the ester moiety. Such polymers aredisclosed, for example, in U.S. Pat. No. 4 341 647 and 4 288 427.

Especially preferred polymers are those wherein the polymer contains

a) 100 to 5 mol % of identical or different structural units of formulaIV ##STR35## and

b) 95 to 0 mol % of identical or different structural units of formula V##STR36## based on said polymer, in which formulae (IV) and (V) R⁷ ishydrogen or methyl, R⁹ is linear or branched C₂ -C₁₈ -alkylene, poly(C₂-C₆ oxaalkylene) containing 2 to 6 oxaalkylene units, C₅ -C₆cycloalkylene, phenylene, benzylene or xylylene or is the group##STR37## Y is --O--, ##STR38## or --N(C₁ -C₄ alkyl), and R¹² is C₁ -C₁₈alkyl, C₅ -C₇ cycloalkyl, (C₁ -C₁₂ alkyl)-C₅ -C₇ cycloalkyl, phenyl, (C₁-C₁₂ alkyl)phenyl, benzyl or (C₁ -C₁₂ alkyl)benzyl, R⁹ is hydrogen, C₁-C₆ alkyl, --COOR¹² or --COO.sup.⊖, R¹⁰ is hydrogen, fluoro, chloro,cyano or C₁ -C₆ alkyl, and R¹¹ is hydrogen, fluoro chloro, cyano, R¹² is--O--, C₁ -C₁₂ alkyl, --COO.sup.⊖, --COOR12, --COOR⁸ --OH, OCO--R¹² orphenyl, where R⁸ and R¹² have the given meanings.

Particularly preferred polymers are those wherein the polymer containsstructural units of formula IV in which R⁷ is hydrogen or CH₃, and R⁸ islinear or branched C₂ -C₆ alkylene, cyclopentylene or cyclohexylene, andstructural units of formula V wherein R⁹ is hydrogen, R¹⁰ is hydrogen ormethyl, and R¹¹ is --COOR¹² or --COOR⁸ --OH.

R⁷ to R¹² and Y have the preferred meanings previously assigned to them,and the preferred content of structural units is likewise as previouslyindicated.

Another embodiment of the invention relates to polymers wherein thethermoplastic polymer is an at least partially sulfated polyvinylalcohol or sulfated polyvinyl alcohol copolymer containing ##STR39##groups. Preferably the composition contains polyvinyl alcoholcopolymers.

Preferred copolymers are those wherein the copolymer contains

a) 90 to 5 mol % of structural units of formula VI ##STR40## and

b) 95 to 10 mol % of identical or different structural units of formulaV ##STR41## in which formulae (VI) and (V) R⁹, R¹⁰ and R¹¹ have themeanings assigned to them above.

Particularly preferred copolymers are those wherein R⁹ and R¹⁰ arehydrogen and R¹¹ is --OCOR¹², wherein R¹² is C₁ -C₁₈ alkyl, C₅ -C₇-cycloalkyl, (C₁ -C₁₂ alkyl)C₅ -C₇ cycloalkyl, phenyl, benzyl, (C₁ -C₁₂alkyl)phenyl or (C₁ -C₁₂ alkyl)benzyl.

R⁹ to R¹² have the preferred meanings previously assigned to them, andthe preferred content of structural units is likewise as previouslyindicated.

Polysiloxanes containing sulfated and hydroxyalkyl groups in salt formare disclosed in JP-A-180690.

Polyimides containing hydroxyl groups are obtainable, for example, fromketotetracarboxylic acids by hydrogenating the keto group prior to thepolyimide formation. Thus, for example, benzophenone-3,4-carboxylic acidanhydride can be converted into bis(benzene-3,4-carboxylic acidanhydride) methanol or the acids or esters thereof.

Sulfated hydroxyl group containing polyesters, polyamides, polyimidesand polyurethanes eligible for use in the practice of this invention maybe prepared by first preparing corresponding unsaturated polymers fromunsaturated monomers, for example unsaturated dicarboxylic acids likemaleic acid or fumaric acid, or from alkenylenediols oralkenylenediamines, for example from 1,4-but-2-ene-diol or1,4-but-2-ene-diamine. The double bonds in the polymers can then beepoxidised--as also in polybutadiene, polyisoprene or chloroprene - withperacids, and the epoxide ring subsequently opened, for example byhydrolysis. The hydroxyl groups can then be sulfated (q.v. for exampleM. L. Hallensleben in Houben Weyl, Vol. E20, page 1994 et seq.).

The thermoplastic polymers eligible for use in the practice of thisinvention can be obtained in known manner by reacting a thermoplastic,film-forming polymer which contains alcohol groups ##STR42## inrepeating structural units, in an inert solvent, with SO₃, subsequentlyneutralising the reaction mixture with an alkali metal base or ammoniumbase, and isolating the polymer.

The process is known per se. The SO₃ can be introduced, for example ingaseous form, into the reaction solution. It is preferred to use apyridine/SO₃ complex which is commercially available.

Suitable inert solvents are preferably polar aprotic solvents, thechoice of solvent depending principally on the solubility of thehydroxyl group containing polymer. The solvents may be used singly or asa mixture of at least two solvents. Illustrative of suitable solventsare: ethers such as dibutyl ether, tetrahydrofuran, dioxan, methyleneglycol, dimethylethylene glycol, dimethyl diethylene glycol, diethyldiethylene glycol, dimethyl triethylene glycol, halogenated hydrocarbonssuch as methylene chloride, chloroform, 1,2-dichloroethane,1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, and lactones such asγ-butyrolactone, o-valerolactone and pivalolactone, carboxamides andlactams such as N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, N-methyl-γ-butyrolactam, N-methyl-ε-caprolactam,N-methylpyrrolidone, N-acetylpyrrolidone, tetramethylurea,hexamethylphosphoramide, sulfoxides such as dimethyl sulfoxide, sulfonessuch as dimethyl sulfone, diethyl sulfone, trimethyl sulfone,tetramethylene sulfone, N-methylpyrrolidine, N-methylpiperidine,N-methylmorpholine, substituted benzenes such as benzonitrile,chlorobenzene, o-dichlorobenzene, 1,2-trichlorobenzene and nitrobenzene.

The reaction temperature is, for example, in the range from 20° to 150°C., preferably from 40° to 100° C. The reaction time is ca. 5 to 10hours. Upon completion of the reaction, the reaction mixture isneutralised, when SO₃ is gaseous form is used, with an aqueous solutionof an alkali metal base or ammonium hydroxide, or with an aqueous ororganic solution of an amine hydroxide. When amine/SO₃ complexes areused, for example a pyridine/SO₃ complex, the corresponding ammoniumsalts are formed, which can be directly used in the electrochemicalprocess. It is also possible to replace the ammonium groups in saidsalts by stronger bases. The salts of the sulfated polymers are usuallyprecipitated with water. The polymer is then isolated by filtration, andcan be purified by washing with water or an organic non-solvent andthereafter dried.

Polyolefins can also be prepared by, for example, radical polymerisationof acrylates and methacrylates containing --O--SO₃ M.sup.⊕ radicals inthe ester moiety, without or together with olefin comonomers.

The eligible salts of sulfated hydroxyl group containing polymers alsohave thermoplastic properties. Compared with the starting polymers,their glass transition temperature is substantially unchanged and theyare distinguished by their mechanical properties, for example by hightensile and flexural strength and high flexibility. They are highlysuitable polyanions for electrically conductive polycations ofpolyheteroaromatic compounds.

Such compositions are prepared in a manner known per se byelectrochemically polymerising, in an aqueous, aqueous-organic ororganic solution, a heteroaromatic compound or an aniline, in thepresence of a sulfated polymer salt, and subsequently removing thecomposition from the anode. The composition is normally deposited as afilm which, depending on the duration of the electrolysis and on thecurrent density, may have a thickness of, for example, 1 to 500 μm or 10to 300 μm.

The electrolysis can be carried out potentiostatically orgalvanostatically. Suitable anode materials are, for example, metals(titanium, nickel, platinum, steel) or ITO glass. The current densitycan be, for example, from 0.5 to 20 mA/cm², preferably from 1 to 5mA/cm².

The concentration of sulfated polymer salt can be from 0.05 to 1 mol/l,preferably from 0.01 to 0.5 mol/l, based on the reaction mixture. Theconcentration of hetero atoms or aniline can be 0.01 to 10% by volume,preferably 0.1 to 5% by volume, based on the volume of the reactionmixture.

Suitable organic solvents are electrochemically inert and, for example,protic or aprotic and polar. Suitable solvents are those listed above.Preferred solvents are carbonates, especially propylene carbonate.

Examples of further suitable solvents are acetonitrile, methylenechloride, propionitrile, nitromethane, and alkanols and water.

A preferred embodiment of the process comprises carrying out thepolymerisation in an organic solvent, M.sup.⊕ being an ammonium cationhaving at least one organic group. M.sup.⊕ is in this connectionpreferably R¹³ R¹⁴ R¹⁵ R¹⁶ N.sup.⊕, wherein R¹³ to R¹⁶ are eachindependently of one another unsubstituted or hydroxyl-substituted C₁-C₁₈ alkyl, phenyl, (C₁ -C₁₂ -alkyl)phenyl, (C₁ -C₁₂ -alkyl)benzyl, C₅-C₇ -cycloalkyl, (C₁ -C₁₂ -alkyl)-C₅ -C₇ -cycloalkyl or R¹³ and R¹⁴,when taken together, are tetramethylene, pentamethylene or3-oxapentylene, and R¹⁵ and R¹⁶ are as previously defined above. Moreparticularly, R¹³ to R¹⁶ are C₁ -C₆ -alkyl, for example methyl, ethyl,n-propyl and, preferably, n-butyl.

The electrochemical polymerisation can also be carried out in water oraqueous-organic solution. The concurrent use of buffers is expedient.Suitable buffers are typically alkylammonium phosphates contatining 1 to3, preferably 2 or 3, alkyl groups in the ammonium moiety, which alkylgroups may contain 1 to 6, preferably 1 to 4, carbon atoms. Examples ofsuitable buffers are trimethylammonium phosphate, triethylammoniumphosphate, tri-n-propylammonium phosphate and tri-n-butylammoniumphosphate. Suitable buffers are also cation exchangers in theirprotonated form.

It is also possible to add to the reaction mixture further substanceswhich deposit concurrently on the anode, for example anionicplasticisers or anionic dyes.

Upon termination of the electrolysis, the compositions of the inventioncan be removed or peeled off from the anode in the form of films andpurified by washing with solvents. The films can be cut to filaments.

The compositions of this invention have high conductivities which areusually above 0.1 S/cm. They further have valuable mechanical propertiessuch as high toughness, tensile strength, flexural strength andflexibility. Surprisingly, it has been found that the compositions ofthis invention have low glass transition temperatures, so that evenwhere polyanion concentration is low, processing by thermoplasticmoulding methods is possible without loss of electrical conductivity.

The compositions of this invention can be used, for example, aselectrical conductors, electrodes, cathodes for batteries,electromagnetic screening materials, electrically conductive filaments,sensors, antistatic packing material, or conductive sealing material.

It has also surprisingly been found that the compositions of thisinvention can be processed by methods for thermoplastic polymers, forexample by moulding methods and, especially, by drawing methods (deepdrawing) below the melting and decomposition temperatures, preferably inthe range of the glass transition temperatures. Besides an increase inmechanical strength, an appreciable, for example an up to five-fold,increase in the electrical conductivity in the direction of drawing hassurprisingly been found.

A further object of the invention is a process for increasing theelectrical conductivity in a film or in filaments of the novelcomposition, which comprises drawing said film or filaments below themelting or decomposition temperature, preferably in the range of theglass transition temperature.

Drawing is preferably carried out at a temperature which is in the rangeof 20° C. below or above the glass transition temperature.

Utilities for the drawn material have been mentioned above in connectionwith non-drawn material. These utilities constitute a further object ofthe invention.

The following Examples illustrate the invention in more detail. Theglass transition temperature (Tg) is determined by differential scanningcalorimetry (DSC). The conductivity is determined by the four-pointmethod. The tensile strength is determined in accordance with DIN 53455.

A) Preparation of sulfated polymer salts EXAMPLE A1

Sulfated polyadduct of bisphenol A diglycidyl ether and bisphenol A(sulfation of all OH groups)

28.4 g of polyadduct having an average molecular weight of 26 800(degree of polymerisation ca. 100) are dissolved at 50° C. in 150 ml ofdimethyl formamide (DMF). To this solution are added 17.5 g of sulfurtrioxide/pyridine complex in 20 ml of DMF. After 5 hours, the reactionmixture is cooled to 5° C. and a solution of 88 g of (n-C₄ H₉)₄ N.sup.⊕OH.sup.⊖ ×30 H₂ O in 100 ml of DMF is added. The reaction mixture ispoured into water and the precipitated polymer salt is isolated byfiltration, washed with water and dried. Yield: 50 g (83 % of theory) ofpolymer salt with a Tg of 87° C.

EXAMPLE A2

Sulfated linear polyadduct of bisphenol A diglycidyl ether and bisphenolA (sulfation of every third OH group)

28.4 g of polyadduct according to Example 1 in 100 ml of DMF, 5.3 g ofsulfur trioxide/pyridine complex and 29.3 g of (n-C₄ H₉)₄ N.sup.⊕OH.sup.⊖ ×30 H₂ O in 50 ml of DMF are reacted and worked up as describedin Example 1. Yield: 28.6 g (73 % of theory) of polymer salt with a Tgof 99° C.

EXAMPLE A3

Sulfated linear polyadduct of bisphenol A diglycidyl ether and bisphenolA (sulfation of every fifth OH group) 284 g of polyadduct according toExample 1 in 400 ml of DMF, 33.4 g of sulfur trioxide/pyridine complexand 160 g of (n-C₄ H₉)₄ N.sup.β OH.sup.⊖ ×30 H₂ O in 100 ml of DMF arereacted and worked up as described in Example 1. Yield: 89 % of theory)of polymer salt with a Tg of 101.5° C.

EXAMPLE A4

Copolymer (10:1) of methyl methacrylate and 3-sulfatopropylmethacrylatetetrabutylammonium salt

43.3 g of a copolymer (10:1) of methyl methacrylate and 3-hydroxypropylmethacrylate are dissolved at 50° C. in 300 ml of DMF. To this solutionare added 7.26 g of sulfur trioxide/pyridine complex. After 5 hours, thereaction mixture is cooled to 5° C. and neutralised withtetrabutylammonium hydroxide 30-hydrate in 30 ml of DMF. The reactionmixture is poured into water and the precipitated product is isolated byfiltration and dried, affording 45.3 g (80.3 % of theory) of polymersalt with a Tg of 127.6° C. The melting point is 193° C.

EXAMPLE A5

Copolymer (1:1) of methyl methacrylate (MMA) and3-sulfatopropylmethacrylate tetrabutylammonium salt

45 g of a 1:1 copolymer of MMA and 3-hydroxypropyl methacrylate aredissolved at 50° C. in 300 ml of DMF. To this solution are added 33.96 gof sulfur trioxide/pyridine complex. After 5 hours, the reaction mixtureis cooled to 5° C. and neutralised with tetrabutylammonium hydroxide30-hydrate (170 g in 200 ml of DMF). The reaction solution is pouredinto water and the precipitate is isolated by filtration and dried,affording 87 g (81.3 % theory) of polymer salt with a Tg of 84.6° C.

EXAMPLE A6

Copolymer of 2-tetrabutylammoniumsulfatoethylmethacrylate/methylmethacrylate (1:2)

20 g (44.3 mmol) of 2-tetrabutylammonium sulfatoethyl methacrylate and8.87 g (88.69 mmol) of methyl methacrylate are dissolved in 100 ml ofacetonitrile and the solution is deaerated. After addition of 30 mg ofazoisobutyronitrile, the reaction solution is stirred for 36 hours at60° C. and then concentrated to dryness under vacuum. The residue istaken up in water, the solution is filtered, and the residue islyophilised, Yield: 20.8 g (72 % theory) of copolymer with a Tg of 85.4°C.

EXAMPLE A7

Sulfated polybutadienes

Epoxidisation (every 4th alkene group) 57.5 g (1 mol) ofcis-polybutadiene (Aldrich) are dissolved in 1000 ml of chloroform. Tothis solution are slowly added dropwise 43 g (0.25 mol) of3-chloroperbenzoic acid in 500 ml of chloroform. After stirring for 12hours, the solution is poured into methanol and the precipitated polymeris isolated by filtration and washed repeatedly with methanol.

Hydrolysis of the epoxy groups

The still moist polymer is dissolved in 1000 ml of tetrahydrofuran(THF). To this solution are slowly added 54.3 ml of 36 % HCl. After 12hours, the reaction solution is poured into methanol and theprecipitated polymer is washed repeatedly with methanol and dried undervacuum at 40° C.

Sulfation

The dry polymer is dissolved in 500 ml of DMF and to this solution areadded 39.75 g (0.25 mol) of pyridine/sulfur trioxide complex. After areaction time of 5 hours, the reaction solution is neutralised with46.25 g (0.25 mol) of tributylamine at ca. 10° C. The solution is pouredinto water and the precipitated polymer is treated repeatedly for sometime with water and subsequently dried under a high vacuum. Yield: 110 g(85 % of theory, based on polybutadiene).

    ______________________________________                                        Elemental analysis:                                                           % C        % H     % N     % O   % S   % Cl                                   ______________________________________                                        cal.:  64.5    7.54    2.69  12.28 6.15  6.8                                  found.:                                                                              64.1    7.7     2.7   12.5  5.9   6.5                                  ______________________________________                                    

Tg=-46.1° C.; m/(n+m): 0.25.

EXAMPLES A8 und A9

Polymers with different degrees of epoxidation and sulfation areprepared in similar manner:

    ______________________________________                                        Composition of the copolymer:                                                 n: number of butadiene units                                                  m: number of sulfated butadiene units                                         Example        m/(n + m) Tg/°C.                                        ______________________________________                                        A8             0.16      -48.3                                                A9             0.11      -56.7                                                ______________________________________                                    

EXAMPLE A10

Copolymer of MMA and 10-hydroxydecyl methacrylate

12 6 g (0.126mol) of MMA and 7.38 g (0.03 mol) of 10-hydroxydecylmethacrylate are dissolved in 40 ml of THF. The solution is then warmedto 55° C. Over a period of 3 hours, a solution of 50 ml ofazoisobutyronitrile in 10 ml of THF is added dropwise and, after 20hours at 55° C., the reaction solution is poured into methanol/water toprecipitate the copolymer. Yield: 17 g (85% of theory). Rel. visc.: 0.59dl/g (in chloroform).

Sulfation

15 g (0.0223 mol, based on the copolymer compositions) of the abovecopolymer are dissolved at 50° C. in 100 ml of DMF and to this solutionare added 4.086 g (0.0257 mol) of sulfur trioxide/pyridine complex.After 2 hours, the reaction solution is neutralised with 6.11 ml (0.0257mol) of tributylamine at a temperature below 10° C. The solution ispoured into water and the precipitated polymer is isolated by filtrationand dried at 50° C. under vacuum. Yield: 18.5 g (98.3 % of theory). Tg:148.2° C.

    ______________________________________                                        Elemental analysis:                                                           % C        % H     % N     % O   % S   % H.sub.2 O                            ______________________________________                                        cal.:  60.36   9.44    1.71  24.5  3.92  1.1                                  found.:                                                                              60.2    9.4     2.2   25.3  3.1   1.1                                  ______________________________________                                    

EXAMPLE A11

Copolymer of MMA and 4-hydroxybutyl methacrylate.

The polymer is prepared in accordance with Example 10. Tg: 153.5° C.

    ______________________________________                                        Elemental analysis:                                                           % C        % H     % N     % O   % S   % H.sub.2 O                            ______________________________________                                        cal.:  56.7    8.9     1.89  28.1  4.3   2.4                                  found.:                                                                              56.6    8.8     2.5   27.8  3.9   2.0                                  ______________________________________                                         m/(n + m) = 0.25                                                              m: number of MMA units                                                        n: number of sulfated hydroxybutyl methacrylate units.                   

EXAMPLES A12-A15

Sulfated polymides

Synthesis of the tetracarboxylic acid component (TCC)

0.62 mol of benzophenone-3,4-dianhydride are heated to the boil in 500ml of methanol until a clear solution forms. After cooling to roomtemperature, the keto groups is reduced with hydrogen under normalpressure (catalyst: 1 g of 5 % Pd/C). The catalyst is separated and thesolution is concentrated to dryness. The resultant mixture consisting ofbis[3-carboxy-4-(carbomethoxy)phenyl]methanol and two further isomers isisolated in a yield of 82 % (197.8 g)

Polymerisation

1 mol of TCC (mixture of isomers) and 1 mol of diamine (DA) are added,under nitrogen, to N-methylpyrrolidone such that a 20 % solution isformed. This solution is heated to 180° C. over 1 hour and kept, withstirring, for 10 hours at this temperature. After cooling, the polymeris precipitated by pouring the solution into water.

    ______________________________________                                        Amine component (DA)    Tg/°C.                                         ______________________________________                                        (a)     bis(4-amino-3-methyl-5-                                                                           302                                                       ethylphenyl)methane                                                   (b)     diaminodurol        340 (Tm)                                          (c)     diaminononane       105                                               (c)     1,3-bis(di-n-propylamine)-                                                                         82.4                                                     tetramethyl disiloxane                                                ______________________________________                                    

Sulfation of the polyimides

0.1 mol of polyimide is dissolved in 100 ml of DMF and to the solutionis added 0.12 mol of sulfur trioxide/pyridine complex. After stirringfor 5 hours, the reaction solution is cooled to room temperature andneutralised with 0.12 mol of tributylamine. The solution is poured intowater to precipitate the polymer, which is isolated, washed copiouslywith water, and dried under vacuum.

    ______________________________________                                        Example   polymer with DA    Tg/°C.                                    ______________________________________                                        A12       a                  290                                              A13       b                  328 (Tm)                                         A14       c                  100                                              A15       d                   49.3                                            ______________________________________                                         Tm melt temperature                                                      

B) Preparation of electrically conductive compositions EXAMPLE B1

6 g of polymer according to Example A1 and 5 ml of pyrrole are dissolvedin 200 ml of propylene carbonate. The solution is blanketed withnitrogen for 10 minutes and transferred to an electrolysis cell. At acurrent density of 2 mA/cm², a ca. 200 μm thick film deposits on to theanode over 2 hours. This film is removed from the electrodemechanically. extracted first with ethanol and then with acetonitrile,and dried under vacuum. The conductivity is 8.7 S/cm. The glasstransition temperature (Tg) is 95° C. After drawing the film by 100 % at95° C., the conductivity increases to 47.5 S/cm.

EXAMPLE B2

12 g of a copolymer according to Example A4 and 5 ml of pyrrole aredissolved in 200 ml of propylene carbonate and the solution istransferred to an electrolysis cell. In accordance with Example 7, a 290μm thick film is obtained. The conductivity of the film is 0.75 s/cm.The Tg is 230° C.

EXAMPLE B3

6.4 g of a copolymer according to Example A5 are dissolved in 200 ml ofpropylene carbonate. The solution is blanked with nitrogen for 10minutes and transferred to an electrolysis cell. In accordance withExample 7, a 218 pm thick film is obtained. The conductivity of the filmis 8.07 S/cm. After drawing the film by ca. 30%, the conductivityincreases to 16.5 S/cm. The glass transition temperature is 205° C.

EXAMPLE B4

23 g of partially sulfated polymer according to Example A2, 5.8 g of amixture of phosphoric acid and tributylamine (pH=3.4), 12 ml of pyrroleand 4 ml of water are dissolved in 300 ml of propylene carbonate. Thesolution is saturated with nitrogen and transferred to an electrolysiscell fitted with a rotating Ni anode (A=30 cm²) and a fine steelcathode. After 1 hour and 7 minutes, a 150 μm thick film is deposited ata current density of 2 mA/cm². After extraction with acetonitrile andvacuum drying, the yield is 353 g. The conductivity is 15.9 S/cm. Theglass transition temperature is 110.5° C. By drawing at 100° C., theconductivity changes in the direction of drawing as follows:

    ______________________________________                                        Drawing in % 1.sub.c                                                                         Conductivity in S/cm                                           ______________________________________                                         0             15.9                                                           20             25.3                                                           40             29.4                                                           85             33.1                                                           ______________________________________                                    

EXAMPLE B5

18 g of polymer according to Example A1, 2 g of 2,2'-bithiophene, 2.1 gof a mixture of phosphoric acid and tetrabutylammonium hydroxide(pH=3.4) are dissolved in 300 ml of propylene carbonate and the solutionis transferred, under nitrogen, to an electrolysis cell. After 1 hour, a115 μm thick film deposits on to the Ni anode. The conductivity of thefilm is 5.5·10⁻³ S/cm. The Tg is 107° C.

EXAMPLE B6

11.8 g of partially sulfated polybutadiene according to Example A7 aredissolved in 200 ml of propylene and, after addition of 10 ml ofpyrrole, transferred to the already described electrolysis cell. At acurrent density of 2 mA/cm², a 0.088 cm thick film deposits over thecourse of 2 hours. The conductivity of the film is 12.5 S/cm. Afterdrawing at room temperature by the factor of 2.11, the conductivityincreases in the direction of drawing to 126 S/cm. The elongation atbreak of this film is ca. 211 %, the modulus of elasticity is 387 MPa.Analogous experiments with polybutadienes according to Examples A8 andA9 give films with conductivities (undrawn) in the range of 8-14 S/cm.

EXAMPLE B7

A solution of 5.77 g of the copolymer according to Example A11 and 10 mlof pyrrole in 200 ml of propylene carbonate is reacted electrochemicallyas described in Example B6. After an electrolysis time of 1 hour, a0.012 pm thick film is obtained. The conductivity is 3.7 S/cm. The filmcan be shaped at temperatures of ca. 150° C.

EXAMPLE B8

A solution of 6.44 s of the copolymer according to Example A10 and 10 mlof pyrrole is reacted electrochemically as described in Example B6.After an electrolysis time of 1 hour, a 0.013 cm thick film is obtained.The conductivity is 4.6 S/cm. The film can be shaped at temperatures ofca. 150° C.

EXAMPLE B9

16.7 g of the sulfated polyimide according to Example A12 are dissolvedin 200 ml of propylene carbonate and 10 ml of pyrrole are added to thesolution. After an electrolysis time of 53 minutes (200 As, a 0.006 cmthick film is obtained in accordance with Example B6. The conductivityis 3.9 S/cm.

EXAMPLE B10

7.16 g of the sulfated polyimide according to claim A13 are dissolved in200 ml of propylene carbonate (0.05 molar) and to the solution are added10 ml of pyrrole. In accordance with Example B6, a 0.01 cm thick filmwith a conductivity of 0.32 S/cm is obtained at a charging density of200 As.

EXAMPLE B11

7.66 of the sulfated polyimide according to Example A14 are dissolved in200 ml of propylene carbonate (0.05 molar, and to the solution are added10 ml of pyrrole. In accordance with Example B6, a 0.009 cm thick filmwith a conductivity of 0.7 S/cm is obtained at a charging density of 200As.

EXAMPLE B12

8 g of the sulfated polyimide according to Example A15 are dissolved in200 ml of propylene carbonate (0.05 molar) and to the solution are added10 ml of pyrrole. In accordance with Example B6, a 0.0095 cm thick filmwith a conductivity of 8 S/cm is obtained at a charging density of 200As.

What is claimed is:
 1. .[.A.]. .Iadd.An electrically conductive polymer.Iaddend.composition comprising.[.(a).]. at least one .[.oxidized.].polycationic .Iadd.polymer and at least one polyanionic polymer, whereinthe polycationic polymer is prepared by electropolymerizing, in asolution with the polyanionic polymer, a monomer selected from the groupconsisting of aniline, a 3-C₁ -C₁₂ alkyl-substituted aniline and a.Iaddend.polyheteroaromatic compound which has 5- or 6-membered ringscontaining 1-3 heteroatoms selected from the group consisting of --O--,--S-- and --N---.Iadd., which rings are either unsubstituted orsubstituted on the carbon atoms with C₁ -C₁₆ alkyl .[.or at least oneoxidized polycationic aniline or a 3-C₁ -C₁₂ alkyl-substituted oxidizedpolycationic aniline.]..Iadd.; .Iaddend.and .[.(b) at least onepolyanion of.]. .Iadd.the polyanionic polymer is .Iaddend.a film-formingthermoplastic polymer containing sulfated alcohol groups ##STR43## inrepeating structural units.Iadd., .Iaddend.having a glass transitiontemperature of -100 to +350° C. and a tensile strength of 5 MPa to 1000MPa.Iadd., the polyanionic polymer being selected from the groupconsisting of polyesters, polyester amides, polyurethanes, polyamides,polycarbonates, polyimides obtained from hydroxyl-containing monomers,saponified polymers of vinyl esters and ethers, hydroxylatedpolybutadiene, polyisoprene or polychloroprene, polyacrylates orpolymethacrylates containing hydroxyl groups in the ester moiety,polysiloxanes containing hydroxyalkyl groups or reduced polyketones,polyadducts of glycidyl compounds containing on average more than oneepoxy group with a diol, and copolymers thereof.Iaddend..
 2. Acomposition according claim 1, wherein the polyheteroaromatic compoundis formed from 5- or 6-membered rings which contain 1 to 3 hetero atomsselected from the group consisting of O, S and N, and the carbon atomsof which are unsubstituted or substituted by C₁ -C₁₆ alkyl.
 3. Acomposition according to claim 2, wherein the 5- 6-membered ring isselected from the group consisting of pyrrole, thiophene, furan,2,2'-bipyrrole, 2,2'-bithiophene, 2,2'-bifurane, thiazole, oxazole,thiadiazole and imidazole.
 4. A composition according to claim 2,wherein the polyheteroaromatic compound is formed from a pyrrole offormula ##STR44## wherein R¹ and R² are each independently of the otherhydrogen or C₁ -C₆ alkyl.
 5. A composition according to claim 1, whichcontains 0.1 to 0.5 structural units containing sulfated alcohol groups##STR45## per structural unit of the polyheteroaromatic compound.
 6. Acomposition according to claim 5, which contains 0.2 to 0.4 structuralunits containing sulfated alcohol groups.
 7. A composition according toclaim 1, wherein the thermoplastic polymer containing sulfated alcoholgroups ##STR46## salt form has a Tg of -100 to +350° C., and M⊕ is analkali metal cation or an ammonium cation.
 8. A composition according toclaim 7, wherein the Tg if -50° to +250° C.
 9. A composition accordingto claim 1, wherein the ratio of free alcohol groups to sulfated alcoholgroup ##STR47## in the thermoplastic polymer is 50:1 to 1:50.
 10. Acomposition according to claim 9, wherein the ratio is 10:1 to 1:10. 11.A composition according to claim 1, wherein the .[.thermoplastic.]..Iadd.polyanionic .Iaddend.polymer is an at least partially sulfatedpolyadduct of a) a glycidyl compound containing on average more than oneepoxy group and b) a diol which contains ##STR48## groups in the polymerchain.
 12. A composition according to claim 11, wherein the polyadductcontainsa) 100 to 5 mol % of identical or different structural units offormula I ##STR49## and b) 95 to 9 mol % of identical or differentstructural units of formula II ##STR50## based on said polyadduct inwhich formulae (I) and (II) above R³ and R⁴ are each independently ofthe other the radical of a diol containing aliphatic or aromatic diolgroups which radical is diminished by two hydroxyl groups, and R' ishydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ acyl or aminocarbonyl which issubstituted by a C₁ -C₂₀ hydrocarbon atom.
 13. A composition accordingto claim
 12. wherein R³ and R⁴ are each independently of the other aradical of formula III ##STR51## wherein X is a direct bond, C₁ -C₄alkylene, C₂ -C₁₂ alkylidene, C₅ -C₈ cycloalkylidene, --O--, --S--,--SO--, SO₂ --, --CO--, --CO₂, --N(C₁ -C₄ alkyl) or --Si(CH₃)₂, R⁵ andR⁶ are each independently of the other hydrogen, halogen, C₁ -C₄ alkyl,or C₁ -C₄ alkoxy, and x is 1 or 2 and y is 0 or
 1. 14. A compositionaccording to claim 12, wherein R³ and R⁴ are the radical ##STR52##
 15. Acomposition according to claim 1, wherein the .[.thermoplastic.]..Iadd.polyanionic .Iaddend.polymer is an at least partially sulfatedhomopolymer or copolymer of acrylates or methacrylates containing a##STR53## group in the ester moiety.
 16. A composition according toclaim 15, wherein the .Iadd.polyanionic .Iaddend.polymer containsa) 100to 5 mol % of identical or different structural units of formula IV##STR54## and b) 95 to 0 mol % of identical or different structuralunits of formula V ##STR55## based on .[.said.]. .Iadd.the polyanionic.Iaddend.polymer, in which formulae (IV) and (V) R⁷ is hydrogen ormethyl, R⁸ is linear or branched C₂ -C₁₈ -alkylene, poly(C₂ -C₆oxaalkylene) containing 2 to 6 oxaalkylene units, C₅ -C₈ cycloalkylene,phenylene, benzylene or xylylene or is the group ##STR56## Y is --O--,##STR57## or --N(C₁ -C₄ alkyl) and R¹² is C₁ -C₁₈ alkyl, C₅ -C₇-cycloalkyl, (C₁ -C₁₂ alkyl)-C₅ -C₇ cycloalkyl, phenyl, (C₁ -C₁₂alkyl)phenyl, benzyl or (C₁ -C₁₂ alkyl)benzyl, R⁹ is hydrogen, C₁ -C₆alkyl, --COOR¹² or --COO⊖, R¹⁰ is hydrogen, fluoro, chloro, cyano or C₁-C₆ alkyl, and R¹¹ is hydrogen, fluoro chloro, cyano, R¹² is --O--, C₁-C₁₂ alkyl, --COO⊖, --COOR¹², --COOR⁸ --OH, --OCO--R¹² or phenyl, whereR⁹ and R¹² have the given meanings.
 17. A composition according to claim16, wherein the polymer contains structural units of formula IV in whichR⁷ is hydrogen or CH₃, and R⁸ is linear or branched C₂ -C₆ alkylene,cyclopentylene or cyclohexylene, and structural units of formula Vwherein R⁹ is hydrogen, R¹⁰ is hydrogen or methyl, and R¹¹ is --COOR¹²or --COOR⁸ --OH. .Iadd.
 18. A composition as set forth in claim 1wherein said polymer is a copolymer containing moieties which areresidues of saponified vinyl esters or ethers, acrylates ormethacrylates containing hydroxyl groups in the ester moiety, orhydroxylated butadiene, isoprene or chloroprene; wherein the monomer hasbeen further copolymerized with a different comonomer selected from thegroup consisting of acrylonitrile, olefins, diolefins, vinyl chloride,vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene,α-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinylesters. .Iaddend. .Iadd.
 19. A composition as set forth in claim 1wherein the polyimide contains residues from hydrogenatedketotetracarboxylic acids. .Iaddend.